物理化学学报 >> 2006, Vol. 22 >> Issue (06): 649-652.doi: 10.3866/PKU.WHXB20060601

研究论文    下一篇

高氯酸碳酰肼钴、高氯酸碳酰肼镍快速热分解反应动力学

孙远华;张同来;张建国;杨利;乔小晶   

  1. 北京理工大学机电工程学院, 爆炸科学与技术国家重点实验室, 北京 100081
  • 收稿日期:2005-10-12 修回日期:2005-10-26 发布日期:2006-05-31
  • 通讯作者: 张同来 E-mail:ztlbit@bit.edu.cn

Kinetics of Flash Pyrolysis of [Co(CHZ3](ClO42 and [Ni(CHZ)3](ClO4)2

SUN Yuan-Hua;ZHANG Tong-Lai;ZHANG Jian-Guo;YANG Li;QIAO Xiao-Jing   

  1. State Key Laboratory of Explosion Science and Technology, School of Mechano-Electronic Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China
  • Received:2005-10-12 Revised:2005-10-26 Published:2006-05-31
  • Contact: ZHANG Tong-Lai E-mail:ztlbit@bit.edu.cn

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摘要： 利用温度跃升傅立叶变换红外原位分析技术(T-jump/FTIR)对高氯酸碳酰肼钴和高氯酸碳酰肼镍的快速热分解反应进行了研究. 研究表明, 目标化合物快速热分解逸出的主要气相产物是CO2, H2O, HCN, HNCO和HONO. 借助快速升温过程中Pt金属丝的控制电压变化曲线得到剧烈放热峰的诱导出现时间tx, 利用tx值计算了两种目标化合物的快速热分解动力学参数. 在0.1 MPa氩气气氛, 613～653 K的实验温度范围内, 高氯酸碳酰肼钴的活化能Ea=39.42 kJ•mol−1, lnA=5.93; 在0.1 MPa氩气气氛, 618～678 K的实验温度范围内, 高氯酸碳酰肼镍的活化能Ea=60.44 kJ•mol−1, lnA=9.40.

关键词: 高氯酸钴, 高氯酸镍, 碳酰肼, 热动力学, 快速热分解, 温度快速跃升傅立叶变换红外光谱

Abstract: T-jump/FTIR spectroscopy was used to study thermal decomposition of energetic material [Co(CHZ)3](ClO4)2 and [Ni(CHZ)3](ClO4)2 in thin film with rapid heating rate. During the exothermic decomposition process, the major gas products were identified as CO2, H2O, HCN, HNCO, and HONO. Time-to-exotherm (tx) kinetics method derived from the control voltage trace of T-jump/FTIR spectroscopy was introduced to resolve kinetics of the exothermic decomposition reaction of flash pyrolysis of the title compounds. In the temperature range of 613～653 K under 0.1 MPa Ar atmosphere the Arrhenius activation energy of the exothermic decomposition reaction of [Co(CHZ)3](ClO4)2 was determined to be Ea=39.42 kJ•mol−1 and lnA=5.93. The Arrhenius activation energy of [Ni(CHZ)3](ClO4)2 was determined to be Ea=60.44 kJ•mol−1 and lnA=9.40 in the temperature range of 618~678 K under 0.1 MPa Ar atmosphere.

Key words: Cobalt perchlorate, Nickel perchlorate, Carbohydrazide, Thermal kinetics, Flash pyrolysis, T-jump /FTIR spectroscopy